CN100344016C - Method for preparing silicon/carbon composite lithium ion battery cathode material under room temperature - Google Patents
Method for preparing silicon/carbon composite lithium ion battery cathode material under room temperature Download PDFInfo
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- CN100344016C CN100344016C CNB2005100295742A CN200510029574A CN100344016C CN 100344016 C CN100344016 C CN 100344016C CN B2005100295742 A CNB2005100295742 A CN B2005100295742A CN 200510029574 A CN200510029574 A CN 200510029574A CN 100344016 C CN100344016 C CN 100344016C
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a method for preparing silicon/carbon composite negative electrode material of a lithium ion battery at room temperature. The present invention is characterized in that the hydrogen and the oxygen of a pre-dispersed silicon /carbohydrate precursor material are removed in the form of water in situ by concentrated sulfuric acid to directly obtain the silicon /carbon composite material, wherein the content range of the silicon in the silicon/carbon composite material is from 5 wt% to 82 wt%, the prior range is from 20 wt% to 30 wt%, and the time of dehydration and carbonization of the concentrated sulfuric acid is 2 hours. The capacity of the silicon/carbon composite negative electrode material containing 20 wt% of silicon prepared by adopting the method for the lithium ion battery is attenuated by only 30% after 10 cycles, which is obvious improvement by being compared with the phenomenon that the capacity of a pure silicon material is attenuated by 99% after 10 cycles.
Description
Technical field
The present invention relates to prepare under a kind of room temperature the method for silicon/carbon composition lithium ion battery cathode material, belong to field of electrochemical power source.
Background technology
Since lithium secondary battery anode is done with material with carbon element substituted metal lithiums such as graphite first by nineteen ninety Sony company, and successfully realized since the commercialization, because the finite capacity of graphite type material (theoretical capacity has only 376mAh/g), people are being devoted to seek good cycle always, the negative material that capacity is higher.The dendrite problem of lithium anode in charge and discharge process never solved at all, can not be applied to serondary lithium battery in a short time.And,, do not exist the problem of dendrite to make silicon become the substitute of carbon class negative material the best because silicon has very high specific capacity (4200mAh/g) with respect to lithium yet.The research work of adopting thin film silicon to do negative pole has obtained very big progress, and is that the research of active material does not have very big breakthrough with the silica flour.Its reason has two: the one, and the intrinsic conductivity of silicon is low; The 2nd, huge change in volume (greater than 300%) in the removal lithium embedded process.The former can make active material lose to electrically contact, and causes the internal resistance of cell to rise; The latter can destroy the mechanical stability of electrode material.The two finally all can cause the electrode cycle performance to descend.The optimal solution that proposes is exactly that silica flour is evenly dispersed in the little matrix of a kind of bulk effect at present, and carbon will be best matrix candidate material undoubtedly.Since it self light weight, and have certain reversible capacity, can not cause declining to a great extent of composite material specific capacity after the adding, moreover the volume of carbon in the removal lithium embedded process is flexible very little, can cushion the change in volume of silica flour effectively, keep the integrality of material.Mainly concentrate on both direction about silicon/carbon composite preparation, a kind of is to adopt chemical vapor deposition (CVD) method heating benzene or toluene gas, makes it deposit formation " hud typed " structure above silica flour; Another kind is that silica flour is dispersed in the acetone soln that is dissolved with pitch, polyvinyl chloride (PVC) etc., treats directly to obtain " cake type " structure by pyrolytic reaction after the solvent evaporates.Though its cycle performance of composite material that adopts these two kinds of methods to obtain is compared all with pure silicon and is greatly improved.The common drawback of these two kinds of methods is exactly operating temperature height (near 1000 ℃), continue to improve temperature and can further improve cycle performance, but silicon and carbon but can react the SiC that generation does not have electro-chemical activity.And the oxidation of silicon also will be used inert atmosphere (N in the operating process under the high temperature
2Even reducibility gas is (as H or Ar),
2) protect.This just makes these two kinds of preparation methods can only be confined to the laboratory, is difficult to realize large-scale production.
Summary of the invention
The object of the present invention is to provide the method for preparing silicon/carbon composite under a kind of room temperature, simplify the operation, reduce cost.Its principle is exactly to utilize the characteristic of the concentrated sulfuric acid---dehydration property, and hydrogen during scattered in advance silicon/carbohydrate forerunner is expected and oxygen carry out original position and remove with the form of water under the room temperature, directly obtain silicon/carbon composite.
Carbohydrate involved in the present invention can be used C
mH
2nO
nExpression, wherein m and n are respectively carbon atom and the oxygen atomicity that contains in the organic molecule, and the number ratio of hydrogen atom and oxygen atom is 2: 1.As sucrose etc. all can find be fit to solvent carbohydrate can, carbon content wherein can be expressed as 1200m/ (12m+18n) wt%.The calculating of silicone content is based under the prerequisite that does not have carbon and the loss of siliceous amount in the dehydration carbonization process in the composite material, obtains in conjunction with the carbon content in the carbohydrate.The content range of silicon is 5wt%-82wt% in silicon/carbon composite involved in the present invention, and optimum range is 20wt%-30%, and when silicone content was lower than 5wt%, the specific capacity of composite material did not improve significantly; In fact when silicone content equaled or exceeded 50wt%, composite material was not obvious to the raising of electrode cycle performance.The silica flour average grain diameter of using among the present invention is below 1 micron.The silica flour particle diameter of Shi Yonging is more little in principle, and the cycle performance that makes composite material is good more.In the process of preparation composite material, without any need for protective atmosphere, only need in atmosphere, to get final product, do not need heat in the preparation process, at room temperature can carry out.In the preparation process, earlier carbohydrate (as sucrose) is dissolved in the corresponding solvent (water), again silica flour is joined by proportioning and form suspension-turbid liquid in the carbohydrate solutions, carry out drying after the ultrasonic dispersion, after treating that solvent evaporates fully, at room temperature in the slurry that forms, add the concentrated sulfuric acid, stir, left standstill dehydration carbonization 2 hours.Add low amounts of water dilution back suction filtration, filter the back and be washed till neutrality with deionized water, dry, pulverize, sieving gets final product.
Compare with existing the whole bag of tricks, characteristics of the present invention are:
(1) carbonization temperature is low, and room temperature can be operated;
(2) carry out in the carbonization process atmosphere, without any need for protective gas;
(3) silica flour can be evenly dispersed in the carbon base body;
(4) other chemical reaction does not take place in silicon in the carbonization process, does not generate such as SiC and SiO
2And so on the impurity phase;
(5) sulfuric acid after the charing is realized recycling after concentration;
(6) in the carbonization process not with an organic solvent, do not produce any pernicious gas yet;
(7) operating procedure is simple, equipment requirements not high (acidproof resistance to oxidation gets final product);
(8) running cost is low.
Description of drawings
Fig. 1 is the X-ray diffraction collection of illustrative plates (c) of silicon/carbon composite of obtaining of sucrose (a), sucrose concentrated sulfuric acid carbide (b) and concentrated sulfuric acid charing.
Fig. 2 is the stereoscan photograph of silicon/carbon composite (siliceous 20%) of making by concentrated sulfuric acid charing.
Fig. 3 is to be the voltage curve that active material assembled battery discharges and recharges experiment (b) with pure silicon (a) and silicon/carbon composite (siliceous 20%) respectively.Numeral charge or discharge number of times among the figure.
Embodiment
Below with the substantive distinguishing features and the obvious improvement of the formal specification method provided by the present invention of Comparative Examples and embodiment, but the present invention only is confined to specific embodiment by no means.
As Comparative Examples 1 of the present invention is that silica flour (average grain diameter 0.2 μ m) and acetylene black and Kynoar (PVDF) are made slurry by 60: 20: 20 mass ratio in N-methyl pyrrolidone (NMP) medium, coat on the Copper Foil and carry out drying, make electrode film thus.With metallic lithium foil is to electrode, and U.S. Celgard company polypropylene screen is a barrier film, 1MLiPF
6/ (PC+DMC) (1: 1) be electrolyte, at 0.1mA/cm
2Current density under, discharge and recharge experiment in the voltage range of 0.02-1.5V.Embedding lithium capacity is 3042mAh/g first, and taking off the lithium capacity is 2108mAh/g, and coulombic efficiency is 69%.The 10th time embedding lithium capacity is 13.7mAh/g, and taking off the lithium capacity is 12.1mAh/g, through 10 circulation volumes, 99% (with respect to taking off the lithium capacity first) of having decayed.Explanation is that the electrode capacity decay of active material is very fast with the pure silicon powder.
Embodiment 1: 5 gram silica flours (average grain diameter 0.2 μ m) are joined in the aqueous solution that is dissolved with 2.5 gram sucrose, the mixing drying, to add concentrated sulfuric acid dehydration carbonization 2 hours in the slurry that obtain again, dilution, filtration, washing to neutral final vacuum drying obtain silicon/carbon composite of siliceous 82wt%.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Embedding lithium capacity is 4637mAh/g first, and taking off the lithium capacity is 3505mAh/g, and coulombic efficiency is 76%.The 10th time embedding lithium capacity is 263mAh/g, and taking off the lithium capacity is 250mAh/g, through 10 circulation volumes, 93% (with respect to taking off the lithium capacity first) of having decayed.As seen the cyclical stability of composite material does not obviously improve.As shown in Figure 1 after concentrated sulfuric acid charing, the diffraction maximum of sucrose has disappeared all, obtain amorphous carbon simple substance (b), and in the X-ray diffracting spectrum of the silicon/carbon composite that obtains by concentrated sulfuric acid charing (c) except the diffraction maximum of crystalline silicon, do not find the diffraction maximum of other material, explanation is when carrying out concentrated sulfuric acid charing processing, and chemical reaction does not take place silicon, and still the form with elemental silicon exists.
Embodiment 2: 5 gram silica flours (average grain diameter 0.2 μ m) and 11.9 gram sucrose are obtained silicon/carbon composite of siliceous 50wt% according to the method for embodiment 1, prepare electrode, electro-chemical test is carried out in assembled battery.Embedding lithium capacity is 2504mAh/g first, and taking off the lithium capacity is 1759mAh/g, and coulombic efficiency is 70%.The 10th time embedding lithium capacity is 543mAh/g, and taking off the lithium capacity is 512mAh/g, through 10 circulation volumes, 72% (with respect to taking off the lithium capacity first) of having decayed.As seen the cyclical stability of composite material improves, and the volume buffering effect is still not remarkable.All the other are with embodiment 1.
Embodiment 3: 5 gram silica flours and 47.5 gram sucrose are carried out electro-chemical test according to silicon/carbon composite, preparation electrode, assembled battery that the method for embodiment 1 obtains siliceous 20wt%.Embedding lithium capacity is 1365mAh/g first, and taking off the lithium capacity is 1115mAh/g, and coulombic efficiency is 82%.The 10th time embedding lithium capacity is 838mAh/g, and taking off the lithium capacity is 784mAh/g, through 10 circulation volumes, 30% (with respect to taking off the lithium capacity first) of having decayed.As seen the stable circulation performance of composite material is significantly improved.From stereoscan photograph shown in Figure 2 as can be seen composite material granular be cellular, silicon atom is present in the carbon skeleton that is formed after concentrated sulfuric acid dehydration by carbohydrate such as sucrose.A large amount of holes that exist can increase the contact area between particle and the electrolyte, help active material electrochemical reaction dynamic process; And from Fig. 3 (a) with find out that (b) cycle-index of the silicon/carbon composite electrode of this component is improved significantly with respect to pure silicon.
Embodiment 4: 5 gram silica flours and 121.8 gram sucrose are carried out electro-chemical test according to silicon/carbon composite, preparation electrode, assembled battery that the method for embodiment 1 obtains siliceous 9.1wt%.Embedding lithium capacity is 1196.5mAh/g first, and taking off the lithium capacity is 745.4mAh/g, and coulombic efficiency is 62.3%.The 10th time embedding lithium capacity is 461.9mAh/g, and taking off the lithium capacity is 436.1mAh/g, through 10 circulation volumes, 41.5% (with respect to taking off the lithium capacity first) of having decayed.As seen continue to reduce silicone content in the composite material, not only reversible capacity reduces, and capability retention also descends to some extent.All the other are with embodiment 1.
Claims (5)
1, the method for preparing silicon/carbon composition lithium ion battery cathode material under a kind of room temperature, it is characterized in that hydrogen and oxygen in scattered in advance silicon/carbohydrate forerunner material with the form of water, carry out original position with the concentrated sulfuric acid under the room temperature and remove, directly obtain silicon/carbon composite.
2, by the method for preparing silicon/carbon composition lithium ion battery cathode material under the described room temperature of claim 1, it is characterized in that specific embodiment is:
(a) earlier carbohydrate is dissolved in the corresponding solvent water, again silica flour is joined by proportioning in the solution of carbohydrate and form suspension-turbid liquid, ultrasonic dispersion, drying;
(b) treat that solvent evaporates fully after, in the slurry that forms, add the concentrated sulfuric acid under the room temperature, stir, leave standstill dehydration carbonization;
(c) add low amounts of water dilution back suction filtration, filter the back and be washed till neutrality with deionized water, dry, pulverize, sieve;
Described carbohydrate is a sucrose;
The weight percentage of silicon is 5-82wt% in described silicon/carbon composite.
3,, it is characterized in that adding that to leave standstill the dehydration carbonization time behind the concentrated sulfuric acid be 2 hours by the method for preparing silicon/carbon composition lithium ion battery cathode material under the described room temperature of claim 2.
4, by the method for preparing silicon/carbon composition lithium ion battery cathode material under claim 2 or the 3 described room temperatures, the weight percentage that it is characterized in that silicon in described silicon/carbon composite is 20-30wt%.
5,, it is characterized in that employed silica flour average grain diameter is below 1 μ m by the method for preparing silicon/carbon composition lithium ion battery cathode material under the described room temperature of claim 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101339987A (en) * | 2008-07-21 | 2009-01-07 | 长沙市海容电子材料有限公司 | Silicon-carbon composite cathode material of lithium ion battery and preparation thereof |
| US10461366B1 (en) * | 2010-01-18 | 2019-10-29 | Enevate Corporation | Electrolyte compositions for batteries |
| CN102887500A (en) * | 2011-07-20 | 2013-01-23 | 刘汉生 | Method for preparing graphene with carbonization surfactant |
| CN103094525B (en) * | 2011-10-28 | 2016-08-03 | 清华大学 | Lithium ion battery negative and preparation method thereof |
| CN103943859B (en) * | 2014-03-13 | 2017-01-18 | 天能电池集团有限公司 | Lead-carbon composite material, and preparation method and application thereof |
| CN104934583B (en) * | 2015-04-17 | 2020-12-08 | 重庆大学 | Preparation method of elemental silicon-graphene nanoribbon composite material |
| TWI594487B (en) * | 2015-04-28 | 2017-08-01 | 烏明克公司 | Composite powder for use in an anode of a lithium ion battery, method for manufacturing a composite powder and lithium ion battery |
| CN105280901B (en) * | 2015-09-23 | 2017-08-11 | 厦门理工学院 | The preparation method of spherical porous silicon carbide composite particles |
| US10326136B2 (en) * | 2015-09-29 | 2019-06-18 | GM Global Technology Operations LLC | Porous carbonized composite material for high-performing silicon anodes |
| CN109616646A (en) * | 2018-12-07 | 2019-04-12 | 上海工程技术大学 | Organic compound/derivative carbon composite preparation method for lithium battery |
Citations (4)
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| JP2002093415A (en) * | 2000-09-18 | 2002-03-29 | Nichia Chem Ind Ltd | Composite carbon material for nonaqueous lithium secondary battery and its synthetic method |
| JP2002260658A (en) * | 2001-03-02 | 2002-09-13 | Samsung Sdi Co Ltd | Carbonaceous material and lithium secondary battery |
| US6589696B2 (en) * | 2000-06-16 | 2003-07-08 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and method of preparing same |
| US6896706B2 (en) * | 2002-01-17 | 2005-05-24 | Korea Institute Of Science And Technology | Carbonaceous materials coated with a metal or metal oxide, a preparation method thereof, and a composite electrode and lithium secondary battery comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6589696B2 (en) * | 2000-06-16 | 2003-07-08 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and method of preparing same |
| JP2002093415A (en) * | 2000-09-18 | 2002-03-29 | Nichia Chem Ind Ltd | Composite carbon material for nonaqueous lithium secondary battery and its synthetic method |
| JP2002260658A (en) * | 2001-03-02 | 2002-09-13 | Samsung Sdi Co Ltd | Carbonaceous material and lithium secondary battery |
| US6896706B2 (en) * | 2002-01-17 | 2005-05-24 | Korea Institute Of Science And Technology | Carbonaceous materials coated with a metal or metal oxide, a preparation method thereof, and a composite electrode and lithium secondary battery comprising the same |
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